Subresinous acylation reaction compound



Patented May 12, .1942

SUBRESINOUS ACYLATION REACTION COMPOUND Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrollte Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing. Original application June 27, 1 940-, Serial No. 342,719. Divided and this application June 14, 1941, Serial No. 398,144

6 Claims.

This invention relates to a new composition of matter, our present application being a division of our parent application Serial No. 342,719, filed June 27, 1940, which resulted in U. S. Patent No. 2,250,406, dated July 22, 1941.

The main object of our'inventionis to provide a new material or composition of matter, that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions, but which may be used for other purposes, or for uses in other arts that we have not yet completely investigated.

Another object of our invention is to provide a. novel method of making the new material or composition of matter above referred to.

The new material or composition of matter which constitutes the subject-matter of our present application can be produced by reacting a polybasic carboxy acid or its functional equivalent, such as the anhydride, and more particularly, phthalic anhydride, with products of the kind derivable by an acylation reaction between amine of the type:

-a ricinoleic acid body and an acylation-reactive Ricinoleic acid is most readily available in the form of castor oil, which contains about 85% triricinolein. Instead of ricinoleic acid, one may employ monoricinolein, diricinolein, methyl ricinoleate, ethyl ricinoleate, benzylricinoleate, cyclohexyl ricinoleate, etc. Similarly, one may employ polyricinoleic acid, such as diricinoleic acid, triricinoleic acid, and tetraricinoleic acid; or one may employ the dibasic type of diricinoleic acid Obviously, ricinoleic acid esters can be derivedfrom polyhydric alcohols other than glycerol, for

instance, from the various glycols, polyglycols.

polyglycerols, methyl glycerol, and the like. ordinarily, one would employ the cheapest source of the ricinoleic acid radical, which is castor oil.

Slightly blown castor oilor, the like may be used.

Castor oil can be treated with one mole or two moles of glycerol, or any intermediate quantity, to produce a material consisting largely of diricinolein, monoricino lein, and some triricin- I olein, with perhaps a small amount of free glyc erol. Such material is commonly referred to as superglycerinated castor oil or superglycerinated triricinolein. Such mixture may be considered as a typical ricinoleic acid body. I

Having indicated the variety of ricinoleic acid compounds which may be employed, reference R: R3

in which R2 is selected from the class consisting of alkylol radicals, alkyl ether radicals, and alkylol ether radicals; Ra may be selected from the class consisting of hydrogen atoms, alkyl radicals, and radicals of the kind exemplified by R2; and R1 represents a member of the class consisting of hydrogen atoms,- alkyl radicals, alkylol radicals, and radicals derived by removal of an alpha hydrogen atom from a carboxy acid ester.

Although such compounds maybe obtained in various ways, obviously they are most readily ane or a homologue or analogue thereof. Thus,

reactions of the kind just referred to, i. 8., intended to producean intermediate product, are concerned with the introduction of an acyl raditween whether an esteriiication reaction takes reaction takes place, or

place, or an amidification if both take place.

will now be made to the type of amine intended for reaction. It is well known that parafllns can be treated with nitric acid, so as to produce nitroparaflins or nitrites. treated with aldehydes, particularly aliphatic aldehydes, having four carbon atoms or less, so as to produce'nitroparamns, in which one, two or three hydroxyl alkyl radicals have been introduced, and particularly characterized by the fact that suchnitroparaflins may have two or three" alkylol groups attached to the same carbon atom. Such nitroparafilns can be readily converted into the corresponding amine. See Chemical Industries," volume 45, No. 7, pages 664 to 668, December, 1939. See also Industrial and Engineering Chemistry, volume 32, No. 1, page 34.

Some known examples of amines of the kind described are:

2-amino 2-methyl-1,3-propanediol cal, for example, a ricinoleyl radical into an amine of the kind mentioned. Such acylation may take Cmoflicmofi place by virtue of an amidiilcation reaction, or

by virtue of an esterification reaction. For the sake of convenience, in the hereto appended 2a'mino'zethyl'l3'propanediol claims, both types of reactions, amidiflcation and NH,

esterification, will be referred to as acylation reactions. In other words, reference to an acyla- 5 CH'OH CH'OH tion reaction is not intended to differentiate be- Tris (hydroxymethyllaminomethane mncwmoma Such nitroparaiilns can be Such amines may be indicated by the following formula type:

in which R represents a divalent radical, such as the methylene radical, and R: may be a hydrogen atom or the same as OI-LR, or may represent a monovalent hydrocarbon radical, particularly an alkyl radical. In other words, the nature of R3 may vary with the particular paraffln selected, and the molalreaction ratio between the nitroparafiln and aldehyde, in the event the paraiiin is methane. Needless to say, such reactions between an aldehyde and a nitroparaflin may yield a monohydric alcohol, as distinguished from a nitro-diol or nitro-triol, in the event the paraflln is methane. Such monobydroxylated compound can be converted into- Such alkylolamine, as, for exan alkylolamine. ample, Z-amino-l-butanol, is not herein contemplated for reaction intended to produce condensation products or esterification products of the kind previously described, i. e., the type to be subsequently reacted with phthalic anhydride or the like. or various aldehydes employed for reaction with the nitroparaiiins, formaldehyde, acetaldehyde, and butyraldehyde are to be preferred, with formaldehyde being particularly desirable. Cyclic aldehydes, such as benzaldehyde, or hexahydrobenzaldehyde, give very inferior yields,

tained from any one of the aldehydes mentioned. for example, acetaldehyde or butyraldehyde; and the butyl radical might be replaced by some other radical, such as the harm radical, benzyl radical, cyclohexyl radical, or the like.

If ethylene oxide, propylene oxide, or the like are used to react with the hydrogen atom previously referred to, then the reaction proceeds as follows:

' alkyl 11.011 H](1J-H0 alkyl aooimon N-OB.0H+ 0 CR.OH alkyl R: alkyl n.

Thus, examining the class of amine compounds in the broadest aspect, they may be rewritten as:

R1 R1 NC 1h Br Ri Having obtained an amine of the kind above described, which is a primary amine, it can readily be converted into a secondary or tertiary,

amine by any of the procedures commonly employed for introducing an alkyl or similar monovalent hydrocarbon radical. By means of suitable alkylating agents, one may introduce alkyl groups, aryl radicals, aralkyl radicals, alicyclic radicals, hydroxy hydrocarbon radicals, and the like. Convenient reagents for such reactions include alkyl chlorides, such as butyl chloride, benzyl chloride, phenyl chloride, ethyl bromide, glycerol chlorhydrin, ethylene chlorhydrin, ethylene oxide, propylene oxide, diethyl sulfate, ethyl chloracetate, etc. The result of an alkylation reaction or the equivalent usually results in the formation of an amine salt, such as the amine hydrochloride. The liberation of the free amine depends upon conventional treatment with caustic soda or the like. Treatment with a reactive allwlene oxide, such as ethylene oxide, propylene oxide, and the like does not resultin the formation of a salt, and thus in many ways is a more suitable procedure. It should be noted that the hydroxyl, which is part of the radical 0H3, is reactive towards alkylating agents. In some instances perhaps such hydroxyl hydrogen atom is more reactive than in the amino hydrogen atom, and perhaps in other instances not so reactive. The speed of the reactions depends, of

course, on the reactants selected and the conditions of the reaction. However, it is to be noted that .such reaction may result in the formation of an ether group. This may be illustrated by involvinga butyl chloride and a hydroxyl hydrogen atom, thus:

. I H R: In this instance the radical 0411003. represents an alkoxyalkyl radical, in which R might be obin which R: represents a monovalent alkylol radical, preferably an alkylol radical, or may be a monovalent oxyhydrocarbon radical, in which the carbon atonr chain is interrupted at least once by an oxygen atom, or may be a hydroxylated oxyhydrocarbon radical, which, in addition to having at least one hydroxyl radical, has the carbon atom chain interrupted at least once by an oxygen atom. Reactants such as glycerol monochlorhydrin, or the corresponding chlorhydrins derived from di- .or triglycerci, would permit the introduction of radicals containing more than one hydroxyl group, and being interrupted more than once by an oxygen atom. R3 may be the same as R2, or atom or any alkyl radical. R1 represents a hydrogen atom, or may represent any alkyl radical, alkylol radical, alkylol-ether, or a radical derived by hypothetical removal of an alpha hydrogen atom from a carboxy acid ester. It is to be noted that the preferred amine is of the -type which contains no aryl radicals, particularly no aryl radicals attached to the amino nitrogen atom, and is preferably of the primary amine type. Due to its availability, the amine which we prefer to employ is tris(hydroxymethyl) aminomethane.

It is obvious, in that the intermediate acylation products obtained may be of the type in which all acyl radicals present are in the amido form. Compounds may be of the type in which all acyl radicals present are in the ester form. It is also possible to have a series of compounds which exhibit both the amido form and the ester form. Furthermore, it is obvious that an amine of the kind contemplated cannot react with a ricinoleic acid body' to give an intermediate acylation product, unless there is present either an alcoholi-iorm hydroxyl,

or an amino hydrogen atom. 01 course, both forms of reactive hydrogen atoms may be present, a hydrogen of the alcohol'radical being referred to as a reactive hydrogen atom. With this in mind, in the hereto'appendedclaims the expression "acylation-reactive amine" is employed to designate such amine; which is reactive in regard to acylation reactions of the kind described. I

As is apparent to a person skilled in the art of acylation reactions of the kind referred to, one can select reactants .and'conditions of reaction,'so asto obtain primarily one particularly type or-primarily another particular type. These variations will be described in some of the following examples: o

may be a hydrogen view of what has been said,

Intermediate product, Example 1 Intermediate product, Example 2 A molecular proportion of trls(hydroxymethyDmethyl butylamine is treated with one mole of ricinoleic acid and heated until one obtains an ester with the elimination of water.

Intermediate product, Example 3 A molecular proportion of tris(hydroxymethyl)methyl butylamine is treated with one mole of ethyl ricinoleate. The esters preferentially react with replacement of an amino hydrogen atom, rather than an alcoholiform hydroxyl hydrogen atom. Thus, the above reaction can be the amide type and the ester type, especially when heated; and theester type is basic and disconducted in a manner to produce the amide in almost complete absence of the ester.

Intermediate product, Example 4 One mole of tris(hydrox'ymethyl)aminome thane is treated with one mole of ricinoleoamide in the conventional manner to eliminate ammonia and form the ricinoleic acid amide of tris(-hydroxymethyl) aminomethane.

Intermediate product, Example 5 One molecular proportion of tris(hydroxymethyl) aminomethane is treated with two moles of ricinoleic acid until one forms the amide ester. Theoretically one can form a secondary amide, i. e., an amide in which two amino hydrogen atoms attached to the same amino nitrogen atom have. been replaced by an acyl radical.

However, the introduction of the second amide group attached to the same amino nitrogen is rather difficult to obtain under ordinary conditions of reaction; and thus, actually one introduces the second acyl group in the ester form.

Intermediate product, Example 6 Tris (butyloxymethyl) aminomethane is treated with one mole of ricinoleic acid to form the corresponding amide of the following .iormula:

oc.n

(cor-001191 However, other means may be employed to obtain predominantly one type or the other. For instance, if one has the amide or a mixture of the amide and ester type, one can convert the same to the ester type by reaction with a dilute acid.

The reason such procedure can be employed is that apparently there is an equilibrium between 75' solves in the acid, thus upsetting the equilibrium. For instance, reference is made to U. S. Patent No. 2,151,788, dated March 28, 1939, to Mauersberger, in which such conversion is illustrated, for instance, in connection with an amide derived from monoethanolamine and oleic acid by use of 85% lactic acid. Such procedure is applicable in connection with the compounds herein contemplated.

Having obtained an esterified amine or an amide or an ester amine of the kind above described, or a mixture of such compounds, the nextstep is to react the same with a polybasic icarboxy acid or its equivalent, such as an anhydride, acyl chloride, or the like. Suitable polybasic carboxyacids include phthalic acid, succinic, maleic, fumaric, citric, maleic, adipic, tartaric, glutaric. diphenic, naphthalic, oxalic, pimelic, suberic, azelaic, sebacic, etc. In the following examples we explain in detail how our new composition of matter may be produced:

Example 1 The method of involve a hydroxyl of an esterified amine, or an ester amide. In other words, the reaction may involve the alcoholiform hydroxyl of the ricino-v leyl radical, or may involve a hydroxyl attached to an alkylradical or the like, such as the hydroxyl of a methylol radical. It is understood, of course, that the reactions may also involve an amino-hydrogen atom, if available, i. e., acylation, as well as esteriflcation, may take place.

As intermediate raw materials, one may employ any'of the intermediate products previously described. Our preference is to use a product of the kind described under the heading Intermediate. product, Example 1," above. Phthalic anhydridc is added to such material in such proportion that one employs one mole of the anhydride for each ricinoleyl radical present. If desired, an increased amount of phthalic anhydride' may'be employed. For instance, one may portions, are added at a temperature of approxiemploy two moles of phthalic anhydride instead of one mole. The mixture of the materials just described, 1. e., the intermediate raw material and phthalic anhydride in predetermined promately -l80 C. until all free phthalic anhy- -dride has disappeared. At. this point one has formed a compound characterized by the factv that there is one free phthalic acid carboxyl present for each mole of phthalic anhydride employed. This stage of reaction is indicated by a determination of the acid value. of the compound obtained depends upon the time of reaction, temperature of reaction, and the molal ratios employed. In other words, one may obtain esterification reactions to a greater degree under one set of circumstances, and perhaps acylation reactions to a greater degree under .slightly -diii'erent circumstances. It is also obvious that one may employ raw materials of the kind described, in which there are no amino hydrogen atoms present; and thus, one obtains no acylation reactions. Under such circumstances the reactions would be strictly of the esteriflcation type.

The final product, which may be a viscous or semi-resinous or sub-resinous material, may be employed as such, ormay be diluted with any suitable solvent of the kind hereinafter described.

reaction for forming said new composition of matter is such as preferably to The nature Erample 2 Maleic acid is substituted for phthalic anhydride in the previous example. Example .3

Succinic acid is substituted for phthalic anhydride in Example 1.

Example 4 An intermediate raw material of the kind described under the heading Intermediate product, Example 4, preceding, is substituted for Intermediate product, in Examples 1-3 preceding.

Example 5 A material of the kind described under the heading Intermediate product, Example 5, preceding, is substituted as a raw material for Intermediate product, in Examples 1-3 preceding.

Example 6 The intermediate material described under the heading Intermediate product, Example 6, preceding, is substituted for Intermediate product, in Examples 1-3 preceding.

Example 7 Example 8 The same procedure is followed as in Example 7 preceding, except that diethanolamine is employed.

Ewample 9 The same procedure is employed as in Example 7, except that the product is heated so as to convert the triethanolamine salt into an ester by reaction involving the carboxylic hydrogen atom of the dibasic acid and a hydroxyl of the ethanol group of the triethanolamine.

Example 10 The same procedure is followed as in Examples 8 and 9 preceding, i. e., diethanolamine is used and one obtains an acylation reaction. However, insofar that diethanolamine is a secondary amine, one probably obtains the mixture of the esterifled amine, the amide, and possibly the ester amide.

It is to be understood that the compounds herein contemplated may be manufactured in any suitable manner, and one is not dependent upon following the exact procedure previously outlined. In certain instances the other reactants might be employed, or else reactants of the kind previously described, might be combined in some other manner. It is not intended that the hereto appended claims be limited in any manner whatsoever as to thejmethod of manufacture, unless such method is' specifically recited.

In such instances where the ricinoleic acid acylation product (an amide, amino or esterifled amine) contains at least two hydroxyl radicals, or at least two amino hydrogen atoms, or at least, one hydroxyl and at least one amino hydrogen atom, then one is dealing with a polyfunctional or bifunctional compound, and thus reactions involving such types of compounds with a polybasic or dibasic acid, such as phthalic anhydride, will produce a sub-resinous or semi-resinous type of material. Compare analogous reactions involving glycerol or glycol or monoethanolamine and dibasic or polybasic acids. Our preferred reagent is derived from an amine of the kind which is polyfunctional, and is most desirably of the sub-resinous type; in other words, a compound or mixture of compounds which still represents a liquid or plastic or fusible mass at a temperature at which the final reaction is completed, and is soluble in one or more solvents which may be hydrophile or hydrophobe in nature, including solutions of an acid, such as acetic acid, hydrochloric acid, etc.

Certain obvious functional equivalents suggest themselves and need not be described in detail. For instance, a halogenated ricinoleic acid body might be employed just as advantageously as an ordinary ricinoleic acid body. No advantage would be obtained by the use of more expensive raw material. Similarly, "chlorinated phthalic anhydride or acid might be used in place of the less' expensive raw material.

It is hardly necessary to indicate that various members of the class previously described are characterized by the presence of a basic or moderately basic amino nitrogen atom, for instance, the ester type. Such basic type of compound naturally can be used as such (without reaction with water) or it can be used in the form of a base, i. e., the compound derived by reaction with water, or in the form of a salt, for instance, the acetate or the salt derived by reaction with a strong mineral acid, such as hydrochloric acid or the like.

We desire to emphasize that the expressions polybasic carboxy acid" and dibasic carboxy acid, used in the claims, refer not only to the acids themselves, but to any functionalequivalent, such as the anhydride, the acyl chloride, a salt form having at least two free carboxyls, such as monosodium citrate, etc.

It is also understood that in the hereto appended claims the nature of the final product is not limited to the form having a free carboxylic hydrogen, but that such free carboxylic hydrogen may actually be replaced by any functional equivalent of the kind previously described, for instance, a metallic atom, an ammonium radical, an amine radical, such as an amylamine radical, benzylamine radical, ethanolamine radical, diethanolamine radical, triethanolamine radical, a hydrocarbon radical, such as an ethyl, methyl, propyl, or amyl radical, a radical derived from ethylene glycol, glycerol, or the like; a cyclohexyl radical, benzyl radical, etc. All such forms in which such ionizable hydrogen atom equivalent replaces an ionizable hydrogen atom, are obvious functional equivalents.

Attention is directed tothe fact that the word amidification" has been applied to the reaction involving the replacement. of an amino hydrogen atom by an acyl radical without conventional limitation to a reaction involving ammonia. The

replacement of the amino hydrogen atom of a primary amine or a secondary amine by an acyl radical has been considered as being'amidiflcasweeten gasoline. See U. S. Patent No. 2,157,223,.

dated May 9, 1939, to Sutton. Certain of the compounds that constitute the above forms of our invention, or which represent difierent examples of the new composition of matter herein described, are also of value as surface tension depressants, or wetting agents in-the flooding of exhausted oil-bearing strata.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A sub-resinous acylation reaction compound, derived by reaction between, first, a polybasic carboxy acid; and second, an amine-of the tor mula:

in which R: is selected from the class consisting of alkylol radicals and alkylol-ether radicals; R3 is selected from the class consisting of hydrogen atoms, alkyl radicals, alkylol radicals and alkylolether radicals; and R1 represents a member of the class consisting of alkylol radicals, alkylol-ether radicals and radicals derived by removal oi-an alpha-hydrogen atom from a monocarboxy acid ester, in which amine at least one reactive hydrogen atom has been replaced by a ricinoleyl radical.

. 2. Asub-resinous acylation reaction compound, derived by reaction between, first, a .dibasic carboxy acide; and second, an amine of the formula: g

RI RI \NO{-R: 31 \RS in which R2 is selected from the class consisting of alkylol radicals and alkylol-ether radicals; R3 is selected from the class consisting of hydrogen atoms, alkyl radicals, alkylol radicals. and alkylol-ether radicals; and R1 represents a memmonocarboxy acid ester, in which amine at least one reactive hydrogen atom has been replaced by a ricinoleyl radical.

3'. A sub-resinous acylation reaction compound,

derived by reaction between, first, a dibasicv carboxy acid; and second, 2-amino-2-methyl-1,3- propanediol,

CHzOHCHzOH Q Hi in which amine at least one reactive hydrogen atom has been replaced by a ricinoleyl radical.

4. A sub-resinous acylation reaction compound,

derived by reaction between, first, a dibasic carboxy acid; and second, 2-amino-2-ethy l-'1,3,-

propanediol,

NH: CHzOHJJCHzOII in which amine at least one reactive hy rogen atom has been replaced by a ricinoleyl radical.

5. A sub-resinous acylation reaction compound,

derived by reaction between, first, a dibasic carboxy acid; and second, tris(hydroxymeth yl)- aminomethane I Nrnc (011203) a in which R: is selected from the class consisting of alkylol radicals and alkvlol-ether radicals:

R3 is selected from the class consisting of hydrogen atoms, alkyl radicals, alkylol radicals and her of the class consisting of alkylol radicals,

allwlol-ether radicals; and R1 represents a member of the class consisting of alkylol radicals, alkylol-ether radicals and radicals derived by removal of an alpha-hydrogen atom from a monocarboxy acid ester, in which amine at least one reactive hydrogen atom has been replaced by a mvm DE (moors.- 

